CN116283310B - Method for printing siloxane precursor ceramic with extremely small curved surface structure based on photocuring 3D - Google Patents
Method for printing siloxane precursor ceramic with extremely small curved surface structure based on photocuring 3D Download PDFInfo
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- 238000007639 printing Methods 0.000 title claims abstract description 48
- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002243 precursor Substances 0.000 title claims abstract description 29
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000005238 degreasing Methods 0.000 claims abstract description 8
- 239000004161 brilliant blue FCF Substances 0.000 claims abstract description 7
- 239000000049 pigment Substances 0.000 claims abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract 2
- 238000011417 postcuring Methods 0.000 claims abstract 2
- 239000002356 single layer Substances 0.000 claims description 14
- 238000010146 3D printing Methods 0.000 claims description 12
- 229920002050 silicone resin Polymers 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y50/00—Data acquisition or data processing for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
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- C04B2235/6567—Treatment time
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Abstract
The invention relates to a method for printing siloxane precursor ceramics with a minimum curved surface structure based on photocuring 3D, which takes organic silicon resin, 405nm wave band photosensitive resin, absolute ethyl alcohol and E133 pigment as raw materials to prepare printing slurry, designs the minimum curved surface structure by using 3ds Max three-dimensional modeling software, introduces the minimum curved surface structure into a 3D printer, sets printing parameters for printing, and carries out ultrasonic washing, ultraviolet post-curing, drying, degreasing and sintering on a printed green body to finally obtain the siloxane precursor ceramics with complex structure, high porosity and excellent mechanical property, and can be applied to the field of electromagnetic wave absorption.
Description
Technical field:
The invention relates to a method for printing siloxane precursor ceramics with a very small curved surface structure based on photo-curing 3D, belonging to the technical field of 3D printing advanced ceramics.
The background technology is as follows:
In recent years, ceramic materials have wide application prospects in important fields of electromagnetic wave absorption, aerospace, national defense and military industry and the like due to excellent mechanical properties, high temperature resistance and corrosion resistance. However, the conventional ceramic powder has disadvantages of high hardness, difficult processing, high sintering temperature, etc., which hampers the possibility of structural design thereof. The precursor ceramic (PDCs) is used as an advanced ceramic, thoroughly changes the pyrolysis method of the traditional ceramic, and provides a new way for directly preparing the ceramic at low temperature. Meanwhile, the PDCs can regulate and control products from the atomic or molecular level, thereby meeting the requirements of personalized ceramic preparation.
3D printing, also called additive manufacturing, is a new process for printing three-dimensional objects layer by layer, has the characteristics of high manufacturing speed, high efficiency, no need of a die and the like, and is suitable for structural design of ceramic materials. The 3D printing paste is prepared by combining a 3D printing technology with PDCs, solid-liquid phase mixing is avoided, the problem of uneven dispersion of traditional ceramic powder in the liquid phase is avoided, and the 3D printing precision is improved. Currently, PDCs have been reported to be prepared using 3D printing techniques such as digital light curing (DLP), direct Ink Writing (DIW), stereolithography (SLA), selective Laser Curing (SLC), two-photon polymerization (TPP), laminated body manufacturing (LOM), and inkjet printing (IJP). The DLP 3D printing and the PDCs are combined, so that the method has the advantages of rapid forming, high printing precision and the like, and has a prospect of preparing ceramics with complex structures.
However, the existing DLP3D printing preparation of ceramics has a plurality of problems, such as complicated process for preparing the DLP3D printing slurry capable of being cured by ultraviolet light at 405nm, sometimes involving complex chemical reaction, uneven shrinkage of a green body after printing and sintering, poor mechanical property and the like. Furthermore, since the application range of structural ceramics is gradually expanding, it has not been limited to models of simple three-dimensional structures. The extremely small curved surface means a curved surface having zero average curvature. Very small curved structures have gained widespread attention due to their maximum specific surface area and their specific pore structure.
At present, a DLP 3D printing technology is utilized to print an extremely small curved surface structure, the printing process is complex, printing slurry involves complex chemical reaction, and the blank body after printing and sintering is unevenly contracted.
The invention comprises the following steps:
Aiming at the defects of the prior art, the invention provides a method for printing siloxane precursor ceramic with a minimum curved surface structure based on photocuring 3D.
The invention is realized by the following technical scheme:
a method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D comprises the following steps:
(1) Designing a minimum curved surface structure by using 3ds Max three-dimensional modeling software, adjusting the wall thickness of the minimum curved surface, and deriving an obtained model in stl format to obtain a minimum curved surface structure model;
(2) Mixing the organic silicon resin and absolute ethyl alcohol, fully stirring, adding 405nm band photosensitive resin, adding E133 pigment after uniformly mixing, enhancing the absorption of the slurry to ultraviolet light, improving the printing precision, obtaining photocuring slurry, placing the photocuring slurry in a dark place for stirring for 10-20 hours, and carrying out vacuum bubble removal in a vacuum drying oven to obtain the slurry to be printed;
(3) Under the condition that the strength, thickness and molding structure of the single-layer cured sample meet the printing requirements, selecting the single-layer exposure time to be 11-13s and the layer thickness to be 40-60um, and introducing the extremely small curved surface structure model in the step (1) into a DLP 3D printer in stl format to start printing to obtain a green body;
(4) Washing the green body, ultraviolet curing, and vacuum drying to obtain a dried green body;
(5) And (3) placing the dried green compact into a sintering furnace, raising the temperature from room temperature to 500-700 ℃, preserving heat for 1-4 hours, degreasing, cooling to room temperature, then sintering, wherein the sintering process is that the temperature is raised from room temperature to 1100-1300 ℃, preserving heat for 1-4 hours, and cooling to room temperature, thus obtaining the siloxane precursor ceramic with the extremely small curved surface structure.
According to a preferred embodiment of the present invention, in step (2), the silicone resin is a methylphenyl silicone resin.
Methyl silicone resin and phenyl silicone resin cannot realize printing.
According to the invention, in the step (2), the mass ratio of the organic silicon resin to the absolute ethyl alcohol is (4-6) to (1-3).
Further preferably, in the step (2), the mass ratio of the organic silicon resin to the absolute ethyl alcohol is 5:2.
The solvent is critical to select, and the solvent is nontoxic and can dissolve the organic silicon resin and 405nm band photosensitive resin into a uniform phase.
According to the invention, in the step (2), the mass ratio of the organic silicon resin to the 405nm band photosensitive resin is 1:1.
According to the invention, in the step (2), the 405nm band photosensitive resin is an epoxy acrylic 405nm band photosensitive resin.
According to the invention, in step (2), the E133 pigment is added so that the mass concentration is 0.1 to 0.3wt%.
According to a preferred embodiment of the invention, in step (3), the printing parameters of the paste are a single layer exposure time of 12s and a layer thickness of 50um.
The single-layer exposure time and the layer thickness of the invention have critical influence on printing, the exposure time is too short, printing is not formed, the exposure time is too long, the printing layer is easy to crack, and the printing efficiency is reduced.
In step (3), the 3D printer is the photo-cured ceramic printer PC5003A-50 and the modeling software used is 3ds Max, which is preferred according to the present invention. Is the prior art.
According to the present invention, preferably, in the step (4), washing is carried out by placing the green compact in a photosensitive resin detergent for ultrasonic cleaning for 5 minutes, removing unreacted 405nm band photosensitive resin, and then washing with absolute ethanol.
According to a preferred embodiment of the present invention, in the step (4), the ultraviolet curing time is 15 minutes.
According to the invention, in the step (4), the vacuum drying is performed in a vacuum drying oven at 80 ℃ for 12 hours.
According to the invention, in the step (5), the degreasing temperature is 600 ℃, the heating rate is 1 ℃/min, and the heat preservation time is 2h.
According to the invention, in the step (5), the sintering temperature is 1200 ℃, the heating rate is 1 ℃/min, and the heat preservation time is 2h.
According to the invention, in the step (5), the whole process is carried out under the atmosphere of N 2, and the cooling rate is 5 ℃/min.
The invention has the technical characteristics and advantages that:
(1) The photocuring paste is the DLP 3D printing paste capable of being cured by ultraviolet light at 405nm, the paste is simple to prepare, does not involve complex chemical reaction, is directly and simply physically mixed, and is high in stability and printability.
(2) The invention utilizes 3ds Max three-dimensional modeling software to prepare a model with a very small curved surface structure and successfully prints out siloxane precursor ceramics, and the raw material used is 405nm photosensitive resin.
(3) The siloxane precursor ceramic with the extremely small curved surface structure has the advantages of complex structure, excellent mechanical property and high porosity, and can be applied to the field of electromagnetic wave absorption.
Description of the drawings:
FIG. 1 is a model of a very small surface structure designed for the 3ds Max of example 1, step (1).
Fig. 2 is a very small curved surface green body physical image after photo-curing 3D printing in step (3) of example 1.
FIG. 3 is a comparative plot of paste print formation at different monolayer exposure times (8 s,10s,12s,15 s).
Fig. 4 is an XRD pattern of the siloxane precursor ceramic obtained in example 1.
FIG. 5 is a thermogravimetric analysis of methylphenyl silicone resin, E133 pigment, green body obtained in step (3) of example 1 and epoxyacrylic 405nm band photosensitive resin.
Fig. 6 is an SEM image of the very small curved green body after photo-curing 3D printing of step (3) of example 1.
FIG. 7 is a graph showing electromagnetic wave-absorbing properties of the siloxane precursor ceramic obtained in example 1.
Detailed Description
In order to fully understand the technical scheme and the beneficial effects of the present invention for those of ordinary skill in the art, the following description is further made with reference to the accompanying drawings and specific embodiments.
The methylphenyl organic silicon resin and the epoxy acrylic acid 405nm band photosensitive resin in the embodiment are all the existing commercial products.
Photosensitive resin cleaners are performed according to the prior art.
Example 1:
a method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D comprises the following steps:
(1) Designing a minimum curved surface structure by using 3ds Max three-dimensional modeling software, adjusting the wall thickness of the minimum curved surface, and deriving a model finally obtained in a stl format;
(2) Preparing 405nm ultraviolet light curing slurry:
200g of methylphenyl organic silicon resin is weighed and dissolved in 80g of absolute ethyl alcohol, 200g of epoxy acrylic acid 405nm wave band photosensitive resin is added into the solution after the solution is completely dissolved, 0.48g of E133 pigment is added after the solution is mixed to enhance the absorption of the slurry to ultraviolet light, the printing precision is improved, the photo-curing slurry is obtained, the photo-curing slurry is wrapped with tinfoil and is protected from light, and the photo-curing slurry is placed in a dark place and stirred for 12 hours; finally, placing the slurry in a vacuum drying oven for vacuum defoaming to obtain slurry to be printed;
(3) DLP 3D prints minimum curved surface structure
The single-layer exposure time is 12s, the layer thickness is 50um,3ds Max software establishes a minimum curved surface structure model, the model is led into a DLP 3D printer in stl format to start printing, after printing is finished, the green body is ultrasonically cleaned for 5min by using a photosensitive resin cleaning agent to remove unreacted 405nm wave band photosensitive resin, then the green body is washed by absolute ethyl alcohol, is put into an ultraviolet oven for curing for 15min to strengthen the strength of the green body, and finally is taken out, put into a vacuum drying oven at 80 ℃ for vacuum drying for 12h and then is taken out; obtaining a dried green body;
(4) Green body degreasing and sintering process
Placing the dried green body into a sintering furnace, degreasing and sintering in the N 2 atmosphere in the whole process, wherein the degreasing process is to raise the temperature from room temperature to 600 ℃, the heating rate is 1 ℃/min, and the heat preservation is carried out for 2 hours; then cooling to room temperature at a cooling rate of 5 ℃/min; the sintering process is to raise the temperature from room temperature to 1200 ℃, the heating rate is 1 ℃/min, and the temperature is kept for 2 hours. Then cooling to room temperature at a cooling rate of 5 ℃/min.
Test example 1:
1. fig. 2 is a real image of a very small curved surface green body printed in the step (3) of example 1 in a photo-curing manner, and it can be seen that the very small curved surface green body printed in the invention has a complex structure, excellent mechanical properties and high porosity.
2. FIG. 4 is an XRD pattern of the siloxane precursor ceramic obtained in example 1, which illustrates that the siloxane precursor ceramic can be successfully obtained by printing and sintering a slurry obtained by simply and physically mixing the organosilicon resin, the absolute ethyl alcohol and the 405 nm-band photosensitive resin according to the invention.
3. FIG. 5 is a thermogravimetric analysis of the components of the photo-curable paste of example 1 and the green body printed.
4. FIG. 7 is a graph showing electromagnetic wave-absorbing properties of the siloxane precursor ceramic obtained in example 1, which illustrates that the siloxane precursor ceramic obtained by printing and sintering a slurry obtained by simply and physically mixing a silicone resin, absolute ethyl alcohol and 405nm band photosensitive resin according to the present invention has excellent electromagnetic wave-absorbing properties.
Comparative example 1
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
step (3), the exposure time of the single layer is 8s.
Comparative example 2
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
step (3), the exposure time of the single layer is 10s.
Comparative example 3
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
Step (3), the exposure time of the single layer is 15s.
Test example 2:
Comparative examples 1-3 and example 1 paste print formation comparisons of 8s,10s,15s,12s at different monolayer exposure times are shown in figure 3.
As can be seen from fig. 3, the exposure time is too short, less than 10s, the printing is not shaped, the exposure time is too long, the printing layer is easy to crack, and the printing efficiency is reduced.
Comparative example 4
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
step (1), methyl silicone resin was used instead of methylphenyl silicone resin, and the procedure of example 1 was followed.
The green body is printed without forming.
Comparative example 5
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
Step (1), phenyl silicone resin was used instead of methylphenyl silicone resin, and the procedure of example 1 was followed.
The green body is printed without forming.
Comparative example 6
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
step (1) was performed as in example 1, except that tetrahydrofuran was used instead of absolute ethanol.
The methylphenyl organic silicon resin and the epoxy acrylic acid 405nm band photosensitive resin cannot be completely dissolved to obtain uniform slurry.
Example 2
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
step (3), the exposure time of the single layer is 13s.
Example 3
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
In the step (1), the dosage of the absolute ethyl alcohol is 100g.
Example 4
The method for printing siloxane precursor ceramics with extremely small curved surface structures based on photo-curing 3D according to example 1 is different in that:
in the step (1), the dosage of the absolute ethyl alcohol is 60g.
Claims (8)
1. A preparation method of siloxane precursor ceramic based on photocuring 3D printing extremely small curved surface structure comprises the following steps:
(1) Designing a minimum curved surface structure by using 3ds Max three-dimensional modeling software, adjusting the wall thickness of the minimum curved surface, and deriving an obtained model in stl format to obtain a minimum curved surface structure model;
(2) Mixing the organic silicon resin and absolute ethyl alcohol, fully stirring, adding 405nm band photosensitive resin, adding E133 pigment after uniformly mixing, enhancing the absorption of the slurry to ultraviolet light, improving the printing precision, obtaining photocuring slurry, placing the photocuring slurry in a dark place for stirring for 10-20 hours, and carrying out vacuum bubble removal in a vacuum drying oven to obtain the slurry to be printed; the organic silicon resin is methyl phenyl organic silicon resin, and the mass ratio of the organic silicon resin to the absolute ethyl alcohol is (4-6) (1-3);
(3) Under the condition that the strength, thickness and molding structure of the single-layer cured sample meet the printing requirements, selecting the single-layer exposure time to be 11-13s and the layer thickness to be 40-60um, and introducing the extremely small curved surface structure model in the step (1) into a DLP 3D printer in stl format to start printing to obtain a green body;
(4) Washing the green body, ultraviolet curing, and vacuum drying to obtain a dried green body;
(5) And (3) placing the dried green compact into a sintering furnace, raising the temperature from room temperature to 500-700 ℃, preserving heat for 1-4 hours, degreasing, cooling to room temperature, then sintering, wherein the sintering process is that the temperature is raised from room temperature to 1100-1300 ℃, preserving heat for 1-4 hours, and cooling to room temperature, thus obtaining the siloxane precursor ceramic with the extremely small curved surface structure.
2. The method according to claim 1, wherein in the step (2), the mass ratio of the silicone resin to the 405nm band photosensitive resin is 1:1.
3. The method according to claim 1, wherein in the step (2), the 405nm band photosensitive resin is an epoxyacrylic 405nm band photosensitive resin.
4. The process according to claim 1, wherein in the step (2), the E133 pigment is added so that the mass concentration is 0.1 to 0.3% by weight.
5. The method according to claim 1, wherein in the step (3), the printing parameter of the paste is a single layer exposure time of 12s and a layer thickness of 50 μm.
6. The method according to claim 1, wherein in the step (4), the green body is washed by ultrasonic cleaning in a photosensitive resin cleaner for 5 minutes, unreacted 405nm band photosensitive resin is removed, then washing is performed with absolute ethyl alcohol, the ultraviolet post-curing time is 15 minutes, and the drying is performed in a vacuum drying oven at 80 ℃ for 12 hours.
7. The method according to claim 1, wherein in the step (5), the degreasing temperature is 600 ℃, the heating rate is 1 ℃/min, and the holding time is 2 hours.
8. The method according to claim 1, wherein in the step (5), the sintering temperature is 1200 ℃, the heating rate is 1 ℃/min, the heat preservation time is 2 hours, and in the step (5), the whole process is performed under the atmosphere of N 2, and the cooling rate is 5 ℃/min.
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